P2s5-epoxide reaction products and salts thereof



United States Patent Office 3,197,404 Patented July 27, 1965 3,197,404 P S -EPOXIDE REACTION PRODUCTS AND SALTS THEREOF Henry G. Berger, Medford Lake, and Herbert Myers, Merchantville, N.J., assignors to Socony Mobil Oil Company, Inc., a corporation of New York No Drawing. Filed June 27, 1961, Ser. No. 119,839 18 Claims. (Cl. 25232.7)

The invention relates to reaction products of phosphorus pentasulfide with epoxides and metal salts thereof and to a method for preparing the same. It relates further to liquid lubricating oil compositions containing these re action products and salts. It is well known that lubricating oils of both the petroleum and synthetic type are subject to oxidative deterioration, particularly under conditions of high temperature and pressure encountered in use in internal combustion engines. This oxidation produces acidic bodies in the oil which are corrosive to the metal parts of the engine, particularly to certain types of alloys, such as copper-lead bearings, utilized in present day engines. This oxidative deterioration is also attended by deposition of carbonaceous sludge, lacquer and resinous materials which accumulate in the engine, particularly around the piston ring skirts and grooves, so that the operating efliciency of the engine is impaired.

In order to overcome, insofar as possible, the deleterious effects of oxidation in lubricating oils, it has become the practice in the art to fortify such oils with minor amounts of chemical agents, which have the ability to minimize these effects. These agents are known as antioxidants.

It is also well known to those familiar with the art that a lubricating oil such as a mere refined petroleum oil fraction is incapable of maintaining a lubricating film between engaged metallic surfaces where the unit load at the engaged surfaces is extremely high as in the hypoid gears used in motor vehicles.

In accordance with this invention, it has been found that phosphorus pentasulfide will react with epoxide compounds to form phosphorusand surfur-containing products which may be converted to metallic salts and that these products and salts are highly effective as antioxidants and extreme pressure agents for mineral lubricating oil. As far as is known, the P S -epoxide reaction products and salts provided by the invention have not been known heretofore and they are, therefore, believed to be new compositions of matter. The precise nature of these products and salts is not presently known, however, and they are, therefore, described and claimed herein by their method of preparation.

It is the primary object of this invention to provide a new class of phosphorusand sulfur-containing products and metal salts thereof. It is a further object to provide a method for the preparation of these new materials. Other objects and advantages of the invention will be apparent from the following detailed description of the invention.

Broadly stated, the phosphorusand sulfur-containing products of the invention are prepared by reacting an epoxy compound with phosphorus pentasulfide at a temperature of from about 25 C. to about 200 C., preferably from about 75 C. to about 150 C., for a time sufficient to efiect substantial reaction. The time required for the reaction will, of course, vary depending upon the temperature employed and the particular epoxide compound involved, the higher temperature generally requiring less reaction time. In general the reaction will be completed in from about 1 to about 25 hours.

It has been found that the reaction betwen the epoxide compound and the phosphorus pentasulfide generally involves from about 2 to about 2.5 mols of the epoxide per mol of the phosphorus pentasulfide. In some instances, however, it has been found beneficial from the standpoint of obtaining substantially complete reaction of the epoxide compound to utilize an excess of the phosphorus pentasulfide over these proportions. Accordingly, the proportions of reactants used can suitably vary from, say, about /2 to about 1 mol proportion of phosphorus peutasulfide to 1 mol proportion of epoxide compound.

Since the epoxide-P S products are usually viscous in nature, it is generally desirable to conduct the reaction in a suitable solvent, such as benzene, toluene, xylene, etc.

Metals in general are contemplated as the metal constituents of the salts of the invention. Thus, for example, the salts of sodium, potassium, lithium, calcium, barium, strontium, magnesium, zinc, aluminum, tin, lead, bismuth, molybdenum manganese, iron, cobalt and nickel may be employed. Due to their relatively greater availablility and lesser cost, however, the salts of the metals of Groups I, H and IV of Mendeleeifs Periodic Table of the Elements are preferred. The metal salts of the epoxide- P S products may be prepared by conventional methods, such as (a) hydrolysis in the presence of a metal base, such as a metal oxide, hydroxide or carbonate of the desired metal or (b) formation of the sodium salt and conversion of this salt to the desired metal salt by double decomposition.

As is well known, epoxy compounds or epoxides are characterized by the presence therein of an oxygen bridge between two carbon atoms in a chain which may be connected to one another directly or through one or more carbon atoms, thus:

, o -c m1. o-

where n is an integer from 0 to 3. I

Epoxide compounds having at least one epoxide group and which contains a total of at least about 8 aliphatic carbon atoms so as to provide oil-solubility in the P S reaction products formed therefrom are contemplated in the present invention.

The epoxides may be those obtained by the oxidation of olefinically unsaturated hydrocarbons. As examples of these epoxides, which are generally termed olefin oxides, there may be mentioned octylene oxide, dodecene oxide, hexadecene oxide, octadecene oxide, dicyclo-pentadiene dioxide, alpha pinene oxide, limonene oxide, alkyl-substituted styrene oxides, such as lauryl-styrene oxide, etc. They may also be derived from olefinically unsaturated alcohols, such as 2,3-epoxy 2-ethyl hexanol and 9,10- epoxy octadecanol. They may be epoxides of unsaturated carboxylic acids, such as 9,10-epoxy stearic acid derived from oleic acid, and 9,10-12,l3-di-epoxy stearic acid derived from linoleic acid, epoxy soy bean oil, etc. Also, they may be epoxides of esters in which the epoxide group appears either in the acid or alcohol portion, or both, for example, the octyl, lauryl and octadecyl alcohol esters of 9,10epoxy stearic acid, the 2,3-epoxy 2 ethyl hexanol ester of stearic acid, the 9,10-epoxy ethyl hexanol ester of 9,10-epoxy stearic acid, etc.

Due to the variety of the epoxide compounds suitable for use in the invention a classification thereof by means of a generic chemical formula is extremely difiicult if not, indeed, impossible. It is believed, however, that the nature of the epoxides is well understood by those familiar with the art. It is considered, therefore, that a feasible and readily understood definition of the epoxides contemplated herein is that they are epoxy compounds derived from olefins, alcohols, acids and esters having a total of from about 8 and up to about 40 carbon atoms, at least about 8 of said carbon atoms being aliphatic carbon atoms.

3 A full understanding of the invention will be had from the following examples and tests which illustrate the preparation of typical products contemplated by the invention and their utility as antioxidants and extreme pressure agents in lubricating oil.

EXAMPLE 1.-REACTION OF DODECENE OXIDE AND PHOSPHORUS PENTASULFIDE Seven hundred and thirty-six grams of a commercial dodecene oxide of approximately 90% purity (3.6 mols) were added over a period of about one-half hour to a slurry of 444 grams (2.0 mols) of phosphorus pentasulfide in 2 liters of benzene in a nitrogen atmosphere. The resulting reaction mixture was then refluxed for 9 hours (T=about 80 C.), cooled to room temperature and filtered, whereby 128 grams (0.53 mol) of unreacted phosphorus pentasulfide was recovered. The filtrate was topped to 90 C. with nitrogen blowing whereby the benzene was removed and then to 120 C. under 0.2 mm. of pressure. Under the latter conditions less than grams of distillate, i.e., unreacted dodecene oxide, was recovered. The dodecene oxide charged to the reaction was, therefore, substantially completely reacted. The product thus obtained was a dark red, viscous liquid which had the following analysis:

Percent Phosphorus 8.6 Sulfur 21.2

EXAMPLE 2.REACT ION OF OCTYLENE OXIDE AND PHOSPHORUS PENTASULFIDE Percent Phosphorus 12.0 Sulfur 26.3

EXAMPLE 3.REACTION OF TRI-ISOBUTYLENE OXIDE AND PHOSPHORUS PENTASULFIDE A solution of 183 grams of tri-isobutylene oxide (1.0 mol) in 250 ml. of xylene was heated to reflux (T=about 144 C.) in a nitrogen atmosphere. One hundred fifteen grams (0.52 mol) of phosphorus pentasulfide was then added in small increments over a period of 3 /2 hours. The resulting reaction mixture was further refluxed for 3 hours, cooled and filtered through diatomaceous earth. No significant amount of phosphorus pentasulfide was re covered. The filtered mixture was then topped under vacuum to a final pot temperature of 130 C. at 0.4 mm. of pressure to remove xylene and any unreacted tri-isobutylene. No unreacted tri-isobutylene was recovered. Fifty grams of a paraflinic mineral oil was then added to the residue giving a dark red, viscous product having the following analysis:

Percent Phosphorus 9.6 Sulfur 22.2

EXAMPLE 4.PREPARATION OF A ZINC SALT OF A DODECENE OXIDEPHOSPHORUS PENTA- SULFIDE REACTION PRODUCT was then removed azeotropically over an additional 7 /2 hours and the resulting slurry filtered through diatomaceous earth to remove the excess zinc oxide. The filtrate was then diluted with 50 grams of a paraflinic mineral oil having a viscosity of SUS at 100 F., topped to C. with nitrogen blowing and to C. at 0.6 mm. of pressure and finally filtered through diatomaceous earth to give a clear, viscous, ambered colored product which had the following analysis:

Percent Zinc 2.9 Phosphorus 3.6 Sulfur 14.8

EXAMPLE 5 .PREPARATION OF A SODIUM SALT OF A DODECENE OXIDE-PHOSPHORUS PENTA- SULFIDE REACTION PRODUCT Percent Sodium 2.3 Phosphorus 5.3 Sulfur 19.1

EXAMPLE 6.PREPARATION OF A NICKEL SALT OF A DODECENE OXIDE-PHOSPHORUS PENTA- SULFIDE REACTION PRODUCT A solution of 238 grams (0.24 equivalent) of the sodium salt prepared in Example 5 in 500 ml. of iso-octane was stirred at room temperature for one hour with a solution of 45 grams (0.36 equivalent) of nickel acetate. The resulting mixture was then transferred to a separatory funnel; the aqueous layer removed and the iso-octane solution washed twice with 25 0 ml. portions of water. The residual water was removed azeotropically and the isooctane removed with nitrogen blowing to 110 C. and under 0.1 mm. of pressure to 120 C. Filtration of the residue through diatomaceous earth gave a black, viscous product which analyzed as follows:

Percent Nickel 4.8 Phosphorus 4.0 Sulfur 20.1 Sodium Nil EXAMPLE 7.PREPARATION OF A LEAD SALT OF A DODECENE OXIDE-PHOSPHORUS PENTA- SULFIDE REACTION PRODUCT Percent Lead 11.3 Phosphorus 3.2 Sulfur 12.5 Sodium Nil Evaluation of products as oil additives The utility of the olefin oxide-phosphorus pentasulfide reaction products and salts thereof as antioxidants and extreme pressure agents in lubricating oils has been shown by comparative tests conducted on a base lubricating oil and on the same oil blended with minor amounts of rep resentative reaction products. The tests used were the Catalytic Oxidation Test (C.O.T.) and the SAE Machine Test.

(a) Catalytic oxidation test.This test determines the effectiveness of an additive in preventing catalytic oxidation of an oil. The test procedure is as follows. In a 200 x 25 mm. test tube is placed a 25 cc. sample of test oil having immersed therein (a) 15.6 sq. in. of sandblasted iron wire, (b) 0.78 sq. in. of polished copper wire, (c) 0.87 sq. in. of polished aluminum wire and (d) 0.167 sq. in. of polished lead surface. The oil is heated to a temperature of 260 F. and maintained at this temperature, while dry air is being passed therethrough, at a rate of 18 liters per hour, for 40 hours. The results of the test are reported in terms of stability number of the additive. The stability number is the percentage of additive (in the oil) multiplied by 100, that reduces the N.N. (neutralization number) of the reference oil to a value of 2. Thus, the lower the additive stability number, the more efiective the additive and vice versa. A stability number of 75 or less signifies a very good antioxidant. The test results are presented in Table I.

FIABLE I.iC.O.T. TEST Product added 1 The base oil used in the test was an SAE 20, solvent-refined Pennsylvania oil.

It will be seen from the test results in Table I that the products of the invention are highly effective oil antioxidants.

(b) SAE machine test-This test measures the loadcarrying capacity of a gear lubricant under high-speed, shock conditions. The oil is placed in the machine as lubricant for two steel test rings which are rotated at difierent speeds against each other in the same direction so as to produce a combination of rolling and sliding action while a gradually increasing load is mechanically applied. The main shaft rotates at 500 rpm. and the rubbing ratio is 14.6 to 1. The loading rate is 75 pounds per minute after a 30-second break-in at 20 pounds. The test is continued until seizure occurs. The results are reported as pounds scale reading at the end of the test. A good extreme pressure oil should carry 300 pounds, or more. The maximum load in accordance with the test is 460 pounds. The test results are shown in Table II.

TABLE II.SAE LOAD TEST500 R.P.M.

1 The base oil used was an SAE 90, solvent-refined, Mid-Continent oil.

2 Failed break-in.

From Table II, it will be evident that the products of the invention impart high load-carrying capacity to the oil.

The amount of phosphorus pentasulfide-olefin oxide product or salt thereof to be added to a lubricating oil to improve the antioxidant properties thereof will range from about 0.1% to about 5.0%, about 0.5% to about 2.0% being the usual required amount. For extreme pressure improvement on the other hand, somewhat higher amounts are used, i.e., from about 1% to about 15%, the usual amount being from about 2% to about In general, therefore, the amounts of the products of the invention added to an oil will vary from about 0.1% to about 15%, by weight.

It is contemplated that the products of the invention may be used in lubricating oils in conjunction with other additives designed to impart diflerent improved characteristics to the oil, such as pour point depressants, viscosity index improvers, detergents, foam inhibitors, etc.

Although the invention has been described herein in terms of specific embodiments and examples thereof, it is not intended that the scope thereof be limited in any way thereby, but only as indicated in the following claims.

\Ve claim:

1. As a new composition, of matter, an oil-soluble phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of an epoxy compound having a total of from about 8 to about 40 carbon atoms, at least about 8 of said carbon atoms being aliphatic carbon atoms and (2) maintaining said reaction mixture at a temperature of from about 25 C. to about 200 C. for a period sufiicient to effect reaction between the phosphorus pentasulfide and the epoxy compound and form the phosphorusand sulfur-containing product.

2. As a new composition of matter, an oil-soluble phosphorusand sulfur-containing product produced by the process which comprises 1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of an epoxy compound having a total of from about 8 to about 40 carbon atoms, at least about 8 of said carbon atoms being aliphatic carbon atoms, (2) maintaining said reaction mixture at a temperature of from about 25 C. to about 200 C. for a period sufiicient to effect reaction between the phosphorus pentasulfide and the epoxy compound and form the phosphorusand sulfurcontaining product and (3) converting said product to a metal salt thereof.

3. As a new composition of matter, an oil-soluble, phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of dodecene oxide and (2) heating said reaction mixture to a temperature of from about 75 C. to about C. for a time sufficient to effect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorusand sulfur-containing product.

4. As a new composition of matter, an oil-soluble, phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of octylene oxide and (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time sufiicient to elfect reaction between the phosphorus pentasulfide and the octylene oxide and form the phosphorusand sulfur-containing product.

5. As a new composition of matter, an oil-soluble, phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of tri-isobutylene oxide and (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time sufiicient to effect reaction between the phosphorus pentasulfide and the tri-isobutylene oxide and form the phosphorusand sulfur-containing product.

6. As a new composition of matter, an oil-soluble, phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of dodecene oxide, (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time suificient to effect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorusand sulfur-containing product and (3) converting said product to a metal salt thereof.

7. As a new composition of matter, an oil-soluble, phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) fiom about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of dodecene oxide, (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time suflicient to effect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorusand sulfur-containing product and (3) converting said product to the sodium salt thereof.

8. As a new composition of matter, an oil-soluble, phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of dodecene oxide, (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time sufiicient to elfect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorusand sulfur-containing product and (3) converting said product to the zinc salt thereof.

9. As a new composition of matter, an oil-soluble, phosphorus and sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of dodecene oxide, (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time suflicient to effect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorusand sulfur-containing product and (3) converting said product to the nickel salt thereof.

10. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15%, by weight, of an oil-soluble, phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of an epoxy compound having a total of from about 8 to about 40 carbon atoms, at least about 8 of said carbon atoms being aliphatic carbon atoms and (2) maintaining said reaction mixture at a temperature of from about 25 C. to about 200 C. for a. period suflicient to effect reaction between the phosphorus pentasulfide and the epoxy compound and form the phosphorusand sulfur-containing product.

11. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15%, by weight, of an oil-soluble, phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of an epoxy compound having a total of from about 8 to about 40 carbon atoms, at least about 8 of said carbon atoms being aliphatic carbon atoms, (2) maintaining said reaction mixture at a temperature of from about 25 C. to about 200 C. for a period sufiicient to effect reaction between the phosphorus pentasulfide and the epoxy compound and form the phosphorusand sulfur-containing product and (3) converting said product to a metal salt thereof.

12. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15 by weight, of an oil-soluble phosphorusand sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of dodecene and oxide and (2) heating said reaction mixture to a temperature of from about 75 C. to about C. for a time suflicient to effect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorusand sulfur-containing product.

13. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15 by weight, of an oil-soluble, phosphorus-and sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of octylene oxide and (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time suflicient to effect reaction between the phosphorus pentasulfide and the octylene oxide and form the phosphorus-and sulfur-containing product.

14. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15% by weight, of an oil-soluble, phosphorus-and sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of tri-isobutylene oxide and (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time sufficient to effect reaction between the phorsphorus pentasulfiide and the tri-isobutylene oxide and form the phosphorus-and sulfur-containing product.

15. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15%, by weight, of an oil-soluble, phosphorus-and sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of dodecene oxide, (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time suflicient to effect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorus-and sulfur-containing product and (3) converting said product to a metal salt thereof.

16. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15 by weight,

of an oil-soluble, phosphorus-and sulfur-containing prod-' not produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to.

about 1 mol proportion of phosphorus pentasulfide and (b) about 1 mol proportion of dodecene oxide, (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time suificient to efiect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorus-and sulfur-containing product and (3) converting said product to the sodium salt thereof.

17. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15%, by weight, of an oil-soluble, phosphorus-and sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus penatsulfiide and (b) about 1 mol proportion of dodecene oxide, (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time suflicient to effect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorus-and sulfur-containing product and (3) converting said product to the zinc salt thereof.

18. A mineral lubricating oil composition comprising a major proportion of mineral lubricating oil and a minor proportion, from about 0.1% to about 15%, by weight, of an oil-soluble, phosphorus-and sulfur-containing product produced by the process which comprises (1) forming a reaction mixture comprising (a) from about /2 to about 1 mol proportion of phosphorus pentasulfide and (b) about 1 .mol proportion of dodecene oxide, (2) heating said reaction mixture to a temperature of from about 75 C. to about 150 C. for a time suflicient to effect reaction between the phosphorus pentasulfide and the dodecene oxide and form the phosphorus-and sulfur-containing product and (3) converting said product to the 15 nickel salt thereof.

References Cited by the Examiner UNITED STATES PATENTS 2/58 Canada.

DANIEL E. WYMAN, Primary Examiner.

JULIUS GREENWALD, ALPHONSO D. SULLIVAN,

Examiners.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,197,404

July 27, 1965 Henry G. Berger et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 1, line 42, for "surfur-containing" read sulfur-containing column 2, line 8, for "peutasulfide read pentasulfide column 8, line 4, for dodecene and oxide and'. read dodecene oxide and line 33, for

"phorsphorus'" read phosphor us (SEAL) i Attest:

ERNEJSTFSW. SWIDER r Attesting Officer V EDWARD-J. BRENNER Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,197,404 July 27, 1965 Henry G. Berger et a1.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, line 42, for "surfur-containing" read sulfur-containing column 2, line 8, for "peutasulfide" read pentasulfide column 8, line 4, for "dodecene and oxide and" read dodecene oxide and line 33, for "phorsphorus" read phosphorus Signed and sealed this 25th day of January 1966.

( L) Attest:

ERNEST W. SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

11. A MINERAL LUBRICATING OIL COMPOSITION COMPRISING A MAJOR PROPORTION OF MINERAL LUBRICATING OIL AND A MINOR PROPORTION, FROM ABOUT 0.1% TO ABOUT 15%, BY WEIGHT, OF AN OIL-SOLUBLE, PHOSPHOROUS- AND SULFUR-CONTAINING PRODUCT PRODUCED BY THE PROCESS WHICH COMPRISES (1) FORMING A REACTION MIXTURE COMPRISING (A) FROM ABOUT 1/2 TO ABOUT 1 MOL PROPORTION OF PHOSPHORUS PENTASULFIDE AND (B) ABOUT 1 MOL PROPORTION OF AN EPOXY COMPOUND HAVING A TOTAL OF FROM ABOUT 8 TO ABOUT 40 CARBON ATOMS, AT LEAST ABOUT 8 OF SAID CARBON ATOMS BEING ALIPHATIC CARBON ATOMS, (2) MAINTAINING SAID REACTION MIXTURE AT A TEMPERATURE OF FROM ABOUT 25*C. TO ABOUT 200*C. FOR A PERIOD SUFFICIENT TO EFFECT REACTION BETWEEN THE PHOSPHORUS PENTASULFIDE AND THE EPOXY COMPOUND AND FORM THE PHOSPHORUS- AND SULFUR-CONTAINING PRODUCT AND (3) CONVERTING SAID PRODUCT TO A METAL SALT THEREOF. 